Monoazo dyestuffs



United States Patent MONOAZO DYESTUFFS Franz Frisch, Arlesheim, Switzerland, assignor, by mesne assignments, to Saul & 00., Newark, N. L, as nominee of fidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application, November 15, 1954 Serial No. 469,038

Claims priority, application Switzerland November 19, 1953 6 Claims. (Cl. 260-496) The present invention relates to acid, metallisable monoazo dyestuffs and represents a further development of the invention described in U. S. Patent No. 2,776,960 (patent application Ser. No. 328,511).

The new acid, metallisable monoazo dyestuffs correspond to the general formula OOOH O: NH-Rr /R: SOr-N\ wherein x stands for lower alkyl, aralkyl, a radical of the benzene series or the radical R being hydrogen or lower allgyl, and R" being lower alkyl, cycloalkyl, aralkyl or mononuclear aryl, R and R" having together at most 14 carbon atoms y stands for hydrogen or methyl R stands for hydrogen, methyl or ethyl R stands for hydrogen or lower alkyl, and

R stands for lower alkyl, cycloalkyl, aralkyl or a radical of the benzene series The dyestuffs dissolve in water with orange, red or bluered'colorations, and dye wool from a neutral or weakly acid bath inbrilliant yellowish-red to blue-red shades, which are only slightly altered by after-chroming. Theyare also suitable for dyeing by means of the single bath chroming process. The dyeings obtained are very fast to light, to milling, and to carbonisation.

The new acid, metallisable monoazo dyestufis are ob- "ice Patented June 3, 1 958 tained by coupling one mol of the diazo compound from an amine corresponding to the formula Or-z wherein x and y have the previously defined significances,

with one mol of an aminonaphthalene compound corresponding to the formula aralkyl A large number of amines are therefore suitable to serve in the form of their diazo compounds, for the synthesis of the new metallisable monoazo dyestuffs. As the most important members, mention may be made, for example, of: 2-amin0-4-methylsulfonyl-4'-hydroxy 1.1-diphenylsulfone-3'-carboxylic acid; Z-amino 4 benzylsulfonyl- 4'-hydr0xy 1.1 diphenylsulfone-3-carboxylic acid, 2- amino-4-phenylsulfonyl-4'-hydroxy-1.1 diphenylsulfone- 3'-carboxylic acid; 2-amino- 3-carboxy-4-hydroxy-1.1- diphenylsulfone-4-su1fonic acid-methylamide; Z-amino- 3'-carboxy-4'-hydroxy-l.1 diphenylsulfone 4 sulfonic acid-.cyclohexylamide; Z-amino 3 carboxy-4'-l1ydroxy- 1.1 diphenylsulfone 4 sulfonic acid-phenylamide; 2, amino-3-carboxy 4 hydrox-y 1.1'-dipheny1sulfone-4-, sulfonic acid-dimethylamide; 2 amino 3' carboxy-4'- hydroxy-l.1'-diphenylsu1fone-4-sulfonic acid-(N-ethyl)- phenylamide, and 2-amino-3'-carboxy-4'-hydroxy-1.1- diphenylsulfone-4-sulfonic acid-(N-methyl)-benzylamide.

As aminonaphthalene compounds of the composition (III), there come into consideration, for instance, 2-'

nonaphthalene-S-sulfonic acid-cyclohexylamide, Z-methylaminonaphthalene-S-sulfonic acid-dimethylarnide and 2- methylaminonaphthalene-S-sulfonic acid-(N-ethyl)-phenylamide.

For carrying out the process, the diazo compound derived from the amine (ll) is coupled with the aminonaphthalene compound (III) in a weak mineral acid or organic acid medium, if desired with the addition of an organic'solvent. After coupling is completed, the monoazo dyestufi which is formed is filtered off, if necessary after previously evaporating off the organic solvent, and converted into the ammonium or lithium or sodium or potassium salts by dissolving in dilute aqueous ammonia, or in lithium, sodium, or potassium carbonate solution respectively. The salts thereby formed are salted out, filtered E, and dried.

The following examples illustrate the invention without limiting it. The parts given therein denote parts by weight, the percentages denote percentages by weight, and the temperatures are in degrees centigrade.

diphenylsulfone-3'-carboxylic acid are dissolved in 500 parts of water, to form a neutral solution by addition of sodium hydroxide. The solution is treated with 36 parts of a 20% solution of sodium nitrite, and is then run at a temperature not exceeding withinhalf an hour, into a mixture of 40 parts of concentrated hydrochloric acid, and 200 parts of water. The yellowish diazo compound which is formed soon separates out almost completely. When the diazotisation is completed, the excess of nitrous acid isdecomposed by the addition of urea to the diazo suspension. To the diazo suspension, which is acid to Congo, there is added dropwise at 10-15" a solution of 23 parts of 2-arninonaphthalene-S-sulfonic acid-methylamide in 500 parts of water and parts of concentrated hydrochloric acid. The orange colored monoazo dyestuff which is formed separates out, and after coupling is finished, it is filtered off. By re-dissolving it in hot sodium carbonate solution, salting out, filtering off, and drying, it is obtained as an-orange colored powder, which dissolves in hot Water with a reddish-orange coloration. It corresponds to the formula CO OH and dyes wool by the single bath chroming process in brilliant red-orange shades of excellent fastness to light, very good fastnessto carbonisation, and very good fastness to milling.

Example 2 45 parts of 2-amino-4-benzylsulfonyl-4-hydroxy-1.1- diphenylsulfone-3'-carboxylic acid are diazotized according to the data given in Example 1. When the nitrous acid has disappeared from the yellow diazo suspension which is formed, a solution of 23 parts ofZ-aminonaphthalene-S-sulfonic acid-methylamide in 500 parts of water and 15 parts of concentrated hydrochloric acid, is added to the diazo suspension at 10-15 The orangecolored monoazo dyestuff which is formed, separates out, and after coupling is finished, it is filtered off. By redissolving it in hot sodium carbonate solution, salting out, filtering off, and drying, it is obtained as an orangecolored powder which dissolves in hot water with an orange color. It corresponds to the formula coon SOI-NH-OHI and dyes wool by the single bath chroming processjin bright reddish-orange shades of excellent'fastness to light, very good fastness to carbonisation, and very good fastness to milling.

Example 3 39 parts of 2-amino-3'-carboXy-4-hydroxy-1.1'-diphenylsulfone-4-sulfonic acid-methylamide arediazotized according to the data given in Example 1. The excess of nitrous acid is decomposed by means of aminosulfonic acid; when this excess has disappeared, the yellow diazo compound which has separated out is filtered off, and added with stirring at 10-15 into a solution of 29.8 parts of 2-aminonaphthalene-5-sulfonic acid-phenylamide and 15 parts of crystallized sodium acetate in 300 parts of methyl alcohol. The orange-colored monoazo dyestufi which is formed separates in crystalline form, and is filtered oflf when coupling is completed. By redissolving in a dilute hot sodium carbonate solution, salting out, filtering ofi and drying, it is obtained as an orange colored powder, which dissolves easily in hot water with an orange color. -It corresponds to the formula sm-Nn-O por'ieiits' a solemn (B "andthe" shade ofthe dye ing's tempe at v 1% h urs'while ke ping the wool or; are

of the chromed dyestuffs on wool in column (C):

move; After this timethe dyjstutfhad been completely No. (A).

2 amino 4 methylsulfonyl 4 hydroxy 1.1' dl- 2-methylaminomphthale'lie fi sullonlehcld ifieth- Blulehred.

phenylsul!one-3'-carboxyllc acid. amide. 2 amino 3 carboxy -'4 -hydr xy 1.1 diphenyl sul- 2 amlnonaphthalene sulionic acid methyl- Orange.

ione-4-sulfonic neld-eyclohexylamide. amide. 2 amino 3 carboxy 4' hydroxye. 1.1! dip heny1-sul 2-aminOnaphthalene-B-sulfonlc acid- (N -methyl)- Do.

lone-4-sulfonle acid-methylamide. j phenylamide. p 2 amino- 3 carboxy 4 hydro'xy 1.1 diphenyl sul- 2-methylamlnonaphthalene-i-sulionlc acid-meth- Scarlet.

tone i sulionic acid; (N=ethy1)- henilamide ylam e. 2 ain 0';- 4 mth'ylsulionyl 4 ydroxy .1.1 di- 2-amlnonaphthalene-S-sulionic acid-cyclohexyl- Red-orange.

phenylsullone-3-carbo lie acid. 1' amide. 2 amino 4 ethylsulfony 4' hydroxy- 1.1L; diphenyl- 2-ethylaminonaphthalene-fi-sulfontc acid-methyl- Bluish red.

sullone-3-earboxyltc acid. amide, 1 10, 21. .2 amino 3 4;: phenylsulipnyl 3 4- hydroxy L1 .di- 2faminbnaphthelene-B-sultonic acld-(N-ethyly' Bed.

. phenylsulfone-W-carbbxyllc acid. phenylamide. I 11..." 2 amino 4 (4" methyl) phenyisulionyl 4t hy- 2-aminonaphthalene-5-sulfonic acld-benzylamide. Do. droxy-l.1-diphenyl-sulione-3 -carboxyl1c acid. I 12.. 2 amino 3' earboxy 4' hydroxy 1.1 dlphenyl sul 2-aminonaphthalene-5-sulionic acid-(N-methyl) Orange-red.

lone-t-sulfonie acld-(N-methyl)-pheny1amide. benzylamide. 13.. 2 amino 3 carbon; 4 hydroxy 1 .1 dlphen'yl sul z-methylaminonaphthalene-b-sult'onic acld-eth'yl- Bluish red.

ionei-sulfonic acl ethylamlde. 1 1 amide. 14"..- 2-amino-3 -carboxy 4 -hydroxy 1.1 diphenyl sul 2 methylaminonaphthalene 5 sulionlc acid Do.

fone-4-sulfonic acld-phenylamide. dimeth amideg. I I I 2. 15 2 amino 3 carboxy 4 hydroxy 1.1 diphenyl sul- 2-methylaminonaplithalene fi'sulfonh" held-db Do.

fone-4-sulfonic acld-benz lamide; methylamide. 16 2 amino 3 carboxy 4' ydroxy .1 diphenyl -'sul 2-methylamlnonaphthalene-B-sulfonic acid-di- Do. fone-4-su1phonic acid-( methyl nzylamlde. Y ethylam e. 17 2 amino 8 carboxy 4 h'ydroxy 1; lfiidiphenyl sul 2-aminonaphthalene-5-sulionlc acld-methylamide. Orange. v tone-'i-sulionicacid-(4"-methyl)-phenylamide.

18.--. 2 -,am'lno 3 carb oxy 4 hydroxr-Ll' dlphenyl sul 2-am1nonaphthalene-dsulfonic aeld- (4-methyl) Do.

Jfonegi-sulionic acldrdtmethylamide. phenylamide. 19.. 2--amlno 3 carboxi 4' hydroxy 1i1 diphenyl sul- 2-methylaminonaphthalene-dsulfonlc acid-butyl- Blulsh red.

fone=4 sulfonic acld-d1ethylaitlide1 am e. p 20.. 2 amino 3 carb oxy 4 hydroxj 1.1 dtphenyl sul- 2-aminonaphthaIene-S-sulionic acid-hexylamide. Orange.

fone-i-sulfonic aeid-propylamide. 21... 2 -amlno-3' arboxy 4' hydroxy-d' :methyl; 1.1 di- 2-aminonaphthalene-5-sulfonic acld-methylemide; Do. phenylsulrone-esulrome acid methylamide. 22.-- 2 amino 4 benzylsulfonyl 4f -.hydroxy 7 5 methyl 2-methylaminonephthalene-fi-sultonic acld-meth- Blulsh red.

1.Mdiiihenilsullone-8 carbbxylie-acid. ylamlde.

='Il1e 'follovtiing are formulae of representative products v of the foregoing examples.

Example 4 CODE SOg-NH-CH:

Or-OH:

Example 8 OOOH Or-OHa SOs-NE Example 23 was brought to and the bath kept near the boiling 76 taken up by the wool; the died goods were then thorough ly rinsed with cold water and dried.

I Exampl eid I lijiebathswe're made up froml'parts of each of the dyestufis described in Examples 1 to 22 and a mixture of the following ingredients was used in making up each dyehath: 2 parts of concentrated acetic acid, 10 parts of so dium sulfate and 5000 parts of water. D'yeings were made from each dyebath as follows: 100 parts of prewetted wool were placed into the dyebathwhich was brought to the boil within half an hour and kept near the boiling temperature for 1 hour. Durin this time2 parts of concentrated formic acid were added to the bath} After the dyeing process was complete the bath was'cooled down to" 70 by the addifion'of cold' water arid, 1'- part of potassium bichromate was added to thepath which was then brought to the boil for half an-hourf 'After this chroming operation the dyeing wasrinsed and dried.

Having thus disclosed the invention what is claimed is:

. l. A monoazo dyestufi corresponding to the formula OOOH 'methylphenylamino, N,N-lower dialkylamino, N-lower alkyl-N-benzylamino and N-lower alkyl-N-phenylamino, the substituted amino groups containing a total of not more than 14 carbon atoms, y stands for a member selected from the group consisting of hydrogen and me h 1 t-matte: a mem ense i d fr t e group 1 rT e-m a yeet fs te est the formula mi in tq w-h dms pl. xhimslm l zds 5:11;; m1; 1 2 member selected from the group consisting of hydrogen 1 v and lower alkyl, and R sta1 1ds for 5 member selected 000E I from the group consisting of lower alkyl, cycloalkyl, 5 v aralkyl and phenyl. H .7 V

The zq dyesmfi w mmmd ns t h o mula 0H Y t-f 6. The hmnoazo dyestofi correspont fing to the; formula QPOH, 531'. 1'- I 3. The monoazo glyestufi cortesponding to the jotm'ola fj- 0H m-om-Q The monoazo dyestqff cones bonding to theformula 1 V 

1. A MONOAZO DYESTUFF CORRESPONDING TO THE FORMULA 